CN114497589B - A modified solid oxide fuel cell electrode and in-situ solvent thermal preparation method thereof, and a solid oxide fuel cell - Google Patents
A modified solid oxide fuel cell electrode and in-situ solvent thermal preparation method thereof, and a solid oxide fuel cell Download PDFInfo
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
- H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
- H01M8/126—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing cerium oxide
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M2008/1293—Fuel cells with solid oxide electrolytes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
- H01M4/861—Porous electrodes with a gradient in the porosity
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention provides a modified solid oxide fuel cell electrode, which comprises a solid oxide fuel cell electrode and modified phase nano particles compounded on the solid oxide fuel cell electrode; the material of the modified phase nanoparticle comprises one or more of a single metal oxide, a doped metal oxide and a perovskite-type catalytic material. The invention adopts a solvothermal method to carry out modification, and carries out in-situ growth of modified phase nano particles on the surface of the solid oxide fuel cell to obtain the modified electrode with specific microstructure and structure. The modified electrode polarization impedance is obviously reduced, the output power of the battery is obviously improved, and the preparation method has the advantages of simple process, easy operation, good shape controllability, low reaction temperature and low energy consumption, and is a preparation method of the in-situ modified solid oxide fuel battery electrode with high feasibility.
Description
Technical Field
The invention belongs to the technical field of solid oxide fuel cell electrodes, relates to a modified solid oxide fuel cell electrode and a preparation method thereof, and a solid oxide fuel cell, and particularly relates to a modified solid oxide fuel cell electrode and an in-situ solvothermal preparation method thereof, and a solid oxide fuel cell.
Background
The solid oxide fuel cell (Solid Oxide Fuel Cell, SOFC for short) belongs to the third generation fuel cell, is an all-solid-state chemical power generation device which can efficiently and environmentally-friendly convert chemical energy stored in fuel and oxidant into electric energy at medium and high temperature, has high efficiency, no pollution, an all-solid structure, wide adaptability to various fuel gases and the like, and is the basis of wide application. Of all fuel cells, the SOFC has the highest operating temperature, and belongs to a high temperature fuel cell. In recent years, distributed power stations have become an important component of world energy supply due to their low cost, high maintainability and the like. The exhaust gas generated by the SOFC has high temperature and high utilization value, can provide heat required by reforming natural gas, can also be used for producing steam, can form combined cycle with a gas turbine, and is very suitable for distributed generation. The combined power generation system composed of the fuel cell, the gas turbine, the steam turbine and the like has the advantages of higher power generation efficiency, low pollution and environmental benefit, wide fuel adaptability, high energy conversion efficiency, full solid state, modularized assembly, zero pollution and the like, and can directly use various hydrocarbon fuels such as hydrogen, carbon monoxide, natural gas, liquefied gas, coal gas, biomass gas and the like. In order to meet the sustainable development of social economy and ecology, reduce the emission of carbon dioxide and reduce the consumption of fossil fuel, the development of a renewable clean energy solid oxide fuel cell is always a hot spot of technical research in the field, and the energy conversion efficiency can reach more than 60 percent without being limited by Carnot cycle; the device has the characteristics of small volume, low noise, no pollution, various available fuels, hot spot combined supply and the like, has wide application potential in the aspects of centralized power generation, distributed power generation, auxiliary power supply and combined heat and power supply, has important significance in saving energy, reducing emission and promoting the change of national energy structures, and has wide application prospect as a mobile power supply such as a ship power supply, a traffic vehicle power supply and the like.
The main components of the solid oxide fuel cell unit consist of electrolyte, anode or fuel electrode, cathode or air electrode and connector or bipolar plate. The solid oxide fuel cell operates on the same principle as other fuel cells and in principle corresponds to an "inverse" device for electrolysis of water. The single cell consists of an anode, a cathode and a solid oxide electrolyte, wherein the anode is a place where fuel is oxidized, the cathode is a place where oxidant is reduced, and both the anode and the cathode contain catalysts for accelerating electrochemical reactions of the electrodes. The working is equivalent to direct current power supply, the anode is the negative electrode of the power supply, and the cathode is the positive electrode of the power supply. However, conventional solid oxide fuel cells operate at high temperatures of 800-1000 ℃, but such high temperatures place extremely high demands on the high temperature resistance of the material. Therefore, the operation temperature of the solid oxide fuel cell is reduced to a medium temperature range of 600-800 ℃, the cost can be greatly reduced, the service life of materials and the cell is prolonged, and the commercial competitiveness of the solid oxide fuel cell is improved. However, as the temperature decreases, the resistance of the cathode of the battery increases greatly, so that the battery performance is greatly attenuated. In recent years, the modification of nanoparticles on the surface of an electrode by a solution impregnation method is a common modification method for battery electrodes, and can reduce the polarization impedance of the electrode on the premise of not changing a material system. However, the solution impregnation method often requires repeated impregnation, has complex steps, and requires sintering at a relatively high temperature after impregnation, which causes damage to the electrode itself, and is relatively energy-consuming and time-consuming.
Therefore, how to modify the electrode of the solid oxide fuel cell more conveniently is suitable for industrialized application, reduces the polarization resistance of the electrode without affecting the performance of the cell, has important practical significance, and is one of the problems to be solved by a plurality of prospective researchers in the field.
Disclosure of Invention
In view of the above, the technical problem to be solved by the invention is to provide a modified solid oxide fuel cell composite electrode, a preparation method thereof and a solid oxide fuel cell, in particular to an in-situ solvothermal preparation method of the modified solid oxide fuel cell electrode.
The invention provides a modified solid oxide fuel cell electrode, which comprises a solid oxide fuel cell electrode and modified phase nano particles compounded on the solid oxide fuel cell electrode;
the material of the modified phase nanoparticle comprises one or more of a single metal oxide, a doped metal oxide and a perovskite-type catalytic material.
Preferably, the solid oxide fuel cell electrode comprises an anode and/or a cathode of a solid oxide fuel cell;
The particle size of the modified phase nano particles is 10-300 nm;
The shape of the modified phase nanoparticle comprises one or more of nanospheres, nanocubes, nanorods and nanoplatelets;
the complexing includes in situ growth.
Preferably, the single metal oxide includes one or more of CuO, ceO 2、Co3O4, and Ag 2 O;
The doped metal oxide comprises Sm doped CeO 2 and/or Gd doped CeO 2;
The perovskite type catalytic material comprises one or more of La 2NiO4、La1-xSrxMnO3 and La 1-xSrxCoO3;
the mass ratio of the modified phase nano-particles to the solid oxide fuel cell electrode compounded by the modified phase nano-particles is (1-30): 100.
Preferably, the modified phase nanoparticles are grown in situ on the solid oxide fuel cell electrode in a uniformly dispersed manner;
the composition on the solid oxide fuel cell electrode comprises composition on the surface of the solid oxide fuel cell electrode and in the holes of the solid oxide fuel cell electrode;
The modified phase nano particles can form a modified phase nano particle layer to be coated on the surface of the solid oxide fuel cell electrode and the surface of the hole of the solid oxide fuel cell electrode.
Preferably, the modification means comprises in situ solvothermal modification;
one or more of the size, morphology and coverage area of the modified phase nanoparticles can be regulated by regulating the conditions of the solvothermal reaction;
the solid oxide fuel cell includes one or more of a cathode symmetrical cell, an anode symmetrical cell, a button cell, and a flat plate cell.
The invention provides a preparation method of a modified solid oxide fuel cell electrode, which comprises the following steps:
1) Mixing a metal salt solution and a pH regulator to obtain a precursor reaction solution;
2) Placing the solid oxide fuel cell or an electrode of the solid oxide fuel cell in the precursor reaction solution obtained in the steps, and vacuumizing to obtain a reaction system;
3) And (3) putting the reaction system obtained in the steps into a reaction device, and performing solvothermal reaction to obtain the modified solid oxide fuel cell electrode.
Preferably, the solvent of the metal salt solution includes a mixed solvent of an organic solvent and water or an organic solvent;
the metal salt comprises one or more of metal nitrate, metal acetate, metal oxalate and metal carbonate;
the pH regulator comprises one or more of propionic acid, acetic acid, oxalic acid, ammonia water and sodium hydroxide;
the pH value of the precursor reaction solution is 3-12;
the precursor reaction solution also comprises a surfactant.
Preferably, the organic solvent comprises one or more of ethanol, ethylene glycol, glycerol, octanol, hexanol, acetone and diethyl ether;
The surfactant comprises one or more of PVP, SDBS and CTAB;
The concentration of the metal salt solution is 0.001-0.5 mol/L;
The volume ratio of the surfactant to the solvent is (0.001-0.3): 1, a step of;
The disposing includes full immersion or half immersion.
Preferably, the vacuum pressure of the vacuumizing treatment is less than or equal to 100KPa;
the temperature of the solvothermal reaction is 100-300 ℃;
The time of the solvothermal reaction is 0.5-36 hours;
the reaction device comprises a hydrothermal reaction kettle.
The invention also provides a solid oxide fuel cell comprising an electrode;
the electrode comprises the modified solid oxide fuel cell electrode prepared by any one of the technical schemes or the preparation method of any one of the technical schemes.
The invention provides a modified solid oxide fuel cell electrode, which comprises a solid oxide fuel cell electrode and modified phase nano particles compounded on the solid oxide fuel cell electrode; the material of the modified phase nanoparticle comprises one or more of a single metal oxide, a doped metal oxide and a perovskite-type catalytic material. Compared with the prior art, the invention aims at the problems that the existing solid oxide fuel cell usually operates at a high temperature of 800-1000 ℃, and extremely high requirements are put on the high temperature resistance of materials, while the operating temperature of the solid oxide fuel cell can be reduced to a medium temperature range of 600-800 ℃, the cost is reduced, the service lives of the materials and the cell are prolonged, but the temperature is reduced, the impedance of the cathode of the cell is greatly increased, and the performance of the cell is greatly attenuated. In addition, the traditional solution impregnation modification method often needs repeated impregnation, has complex steps, needs sintering at relatively high temperature after impregnation, and has the problems of damage to the electrode, high energy consumption, long time consumption and the like.
The modified solid oxide fuel cell electrode prepared by the invention has specific microscopic morphology and structure, specific single metal oxide, doped metal oxide or perovskite type catalytic material modified phase nano particles can be formed on the surface of the electrode, the polarization resistance of the modified electrode is obviously reduced, and the output power of the cell is obviously improved. More importantly, the invention creatively adopts a solvothermal method for modification, and carries out in-situ growth of modified phase nano-particles on the surface of the solid oxide fuel cell. Compared with the traditional solvothermal method, the preparation method has the advantages of simple process, easy operation, good shape controllability, low reaction temperature and low energy consumption, and is a preparation method of the in-situ modified solid oxide fuel cell electrode with high feasibility.
Experimental results show that nanoparticles with different morphologies such as nanospheres, nanocubes and the like can be grown on the surface of the electrode in situ by a solvothermal method, and the size of the nanoparticles can be controlled by regulating and controlling reaction conditions. The modified electrode has more excellent electrochemical performance than a blank electrode, and can reduce polarization resistance by more than 20%.
Drawings
FIG. 1 is a SEM image of a modified solid oxide fuel cell electrode prepared in example 1 of the present invention;
FIG. 2 is an XRD diffraction pattern of the powder isolated from the solvothermal solution in example 1 of the present invention;
FIG. 3 shows Arrhenius curves of polarization resistance of unmodified LSCF electrodes and example 1 of the present invention after solvothermal treatment at different temperatures;
FIG. 4 is a SEM image of the surface of the Co 3O4 modified LSCF composite electrode prepared by the invention;
FIG. 5 is a SEM image of the surface of the Co 3O4 modified LSCF composite electrode prepared by the invention;
Fig. 6 is an XRD diffractogram of the powder isolated from the solvothermal solution in example 4 of the present invention.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention and are not limiting of the invention claims.
All the raw materials of the present invention are not particularly limited in their sources, and may be purchased on the market or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the present invention are not particularly limited in purity, and the present invention preferably employs a conventional purity used in the field of analytical purity or solid oxide fuel cell cathode production.
The invention provides a modified solid oxide fuel cell electrode, which comprises a solid oxide fuel cell electrode and modified phase nano particles compounded on the solid oxide fuel cell electrode;
the material of the modified phase nanoparticle comprises one or more of a single metal oxide, a doped metal oxide and a perovskite-type catalytic material.
The invention is not particularly limited in principle for the selection of the solid oxide fuel cell electrode, and can be selected and adjusted by a person skilled in the art according to practical application conditions, product requirements and quality requirements, and in order to further ensure the specific morphology structure of the composite material, enhance the uniform dispersion of the modified phase material, the solid oxide fuel cell electrode preferably comprises an anode and/or a cathode of a solid oxide fuel cell, more preferably the anode or the cathode of the solid oxide fuel cell, and further preferably reduces the polarization resistance of the cathode, improves the output power of the cell, simplifies the manufacturing process, and enhances the controllability and the operability.
The material of the modified phase nano-particles in the invention comprises one or more of a single metal oxide, a doped metal oxide and a perovskite type catalytic material, and more preferably the single metal oxide, the doped metal oxide or the perovskite type catalytic material.
The invention is not particularly limited in principle, and the specific choice of the single metal oxide is selected and adjusted by a person skilled in the art according to practical application conditions, product requirements and quality requirements, and in order to further ensure a specific morphology structure of the composite material, enhance uniform dispersibility of the modified phase material, better reduce polarization resistance of a cathode, improve output power of a battery, simplify preparation procedures, and enhance controllability and operability, the single metal oxide preferably comprises one or more of CuO, ceO 2、Co3O4 and Ag 2 O, and more preferably CuO, ceO 2、Co3O4 or Ag 2 O.
The specific choice of the doped metal oxide is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to practical application conditions, product requirements and quality requirements, so that the specific morphology structure of the composite material is further ensured, the uniform dispersibility of the modified phase material is enhanced, the polarization resistance of a cathode is better reduced, the output power of a battery is improved, the preparation process is simplified, and the controllability and the operability are enhanced.
The perovskite type catalytic material is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to practical application conditions, product requirements and quality requirements, and in order to further ensure a specific morphology structure of the composite material, enhance uniform dispersibility of a modified phase material, better reduce polarization resistance of a cathode, improve output power of a battery, simplify preparation procedures, and enhance controllability and operability, the perovskite type catalytic material preferably comprises one or more of La 2NiO4、La1-xSrxMnO3 and La 1-xSrxCoO3, and more preferably La 2NiO4、La1-xSrxMnO3 or La 1- xSrxCoO3.
The particle size of the modified phase nano particles is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to practical application conditions, product requirements and quality requirements, and the particle size of the modified phase nano particles is preferably 10-300 nm, more preferably 60-250 nm, and even more preferably 60-100 nm in order to further ensure the specific morphology structure of the composite material, enhance the uniform dispersibility of the modified phase material, better reduce the polarization resistance of a cathode, improve the output power of a battery, simplify the preparation process and enhance the controllability and the operability.
The shape of the modified phase nano particles is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to practical application conditions, product requirements and quality requirements, and the modified phase nano particles are preferably one or more of nanospheres, nanocubes, nanorods or nanoplatelets, more preferably nanospheres, nanocubes, nanorods or nanoplatelets, in order to further ensure a specific morphology structure of the composite material, enhance uniform dispersibility of the modified phase material, better reduce polarization resistance of a cathode, improve output power of a battery, simplify preparation procedures and enhance controllability and operability.
The mass ratio of the modified phase nano particles to the solid oxide fuel cell electrode compounded by the modified phase nano particles is not particularly limited in principle, and can be selected and adjusted according to practical application conditions, product requirements and quality requirements by a person skilled in the art, and the mass ratio of the modified phase nano particles to the solid oxide fuel cell electrode compounded by the modified phase nano particles is preferably (1-30): 100, more preferably (5 to 25): 100, more preferably (10 to 20): 100.
The invention is not particularly limited in principle to the specific manner of compounding, and can be selected and adjusted by the person skilled in the art according to the actual application, the product requirements and the quality requirements, in order to further ensure the specific morphology and structure of the composite material, the uniform dispersibility of the modified phase material is enhanced, the polarization resistance of the cathode is better reduced, the output power of the battery is improved, the preparation process is simplified, the controllability and the operability are enhanced, and the compounding preferably comprises in-situ growth. More specifically, the modified phase nanoparticles are preferably uniformly dispersed grown in situ on the solid oxide fuel cell electrode.
The invention is not particularly limited in principle for the specific state of the composition, and a person skilled in the art can select and adjust the composition according to the actual application situation, the product requirement and the quality requirement, and in order to further ensure the specific morphology structure of the composite material, enhance the uniform dispersibility of the modified phase material, better reduce the polarization resistance of the cathode, improve the output power of the battery, simplify the preparation process, and enhance the controllability and the operability, the composition on the solid oxide fuel cell electrode preferably comprises the composition on the surface of the solid oxide fuel cell electrode and in the holes of the solid oxide fuel cell electrode. More specifically, the modified phase nanoparticle preferably can form a modified phase nanoparticle layer to coat the surface of the solid oxide fuel cell electrode and the surface of the hole of the solid oxide fuel cell electrode.
The modification mode is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to practical application conditions, product requirements and quality requirements, and the modification mode preferably comprises in-situ solvothermal modification in order to further ensure a specific morphology structure of the composite material, enhance uniform dispersibility of a modified phase material, better reduce polarization resistance of a cathode, improve output power of a battery, simplify preparation procedures and enhance controllability.
The invention is a complete and refined integral preparation process, further ensures the specific morphology structure of the composite material, enhances the uniform dispersion of the modified phase material, better reduces the polarization resistance of the cathode, improves the output power of the battery, simplifies the preparation process, enhances the controllability and the operability.
The invention is not particularly limited in principle for the specific selection of the solid oxide fuel cell, and the skilled person can select and adjust the solid oxide fuel cell according to practical application conditions, product requirements and quality requirements, and the invention further ensures the specific morphology structure of the composite material, enhances the uniform dispersion of the modified phase material, better reduces the polarization resistance of the cathode, the solid oxide fuel cell preferably comprises one or more of a cathode symmetrical cell, an anode symmetrical cell, a button cell and a flat plate cell, and more preferably comprises a symmetrical cell, an anode symmetrical cell, a button cell or a flat plate structure cell.
The definition and structure of the symmetrical battery are not particularly limited, the structure and definition of the symmetrical battery are well known to those skilled in the art, and the skilled person can select and adjust the symmetrical battery according to practical application conditions, product requirements and quality requirements, and the symmetrical battery is a half battery commonly used for detection in the art. In the art, a symmetrical battery includes only a cathode or an anode, which is a structure proposed for convenience in studying electrode performance, and can be understood as a half-cell. Whereas conventional batteries include a cathode and an anode, are "full cells",
The invention provides a preparation method of a modified solid oxide fuel cell electrode, which is characterized by comprising the following steps:
1) Mixing a metal salt solution and a pH regulator to obtain a precursor reaction solution;
2) Placing the solid oxide fuel cell or an electrode of the solid oxide fuel cell in the precursor reaction solution obtained in the steps, and vacuumizing to obtain a reaction system;
3) And (3) putting the reaction system obtained in the steps into a reaction device, and performing solvothermal reaction to obtain the modified solid oxide fuel cell electrode.
The selection, composition and structure of the materials in the preparation method and the corresponding preferred principles of the invention preferably correspond to those of the modified solid oxide fuel cell electrode, and the corresponding preferred principles are not described in detail herein.
Firstly, mixing a metal salt solution and a pH regulator to obtain a precursor reaction solution.
The invention is not particularly limited in principle to the specific choice of the solvent of the metal salt solution, and can be selected and adjusted by the person skilled in the art according to the actual application, the product requirements and the quality requirements, in order to further ensure the specific morphology and structure of the composite material, the method has the advantages of enhancing the uniform dispersibility of the modified phase material, better reducing the polarization resistance of the cathode, improving the output power of the battery, simplifying the preparation process, and enhancing the controllability and operability, wherein the solvent of the metal salt solution preferably comprises a mixed solvent of an organic solvent and water or an organic solvent.
The specific choice of the organic solvent is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to practical application conditions, product requirements and quality requirements, and the organic solvent is preferably one or more of ethanol, glycol, glycerol, hexanol, acetone and diethyl ether, more preferably ethanol, glycol, glycerol, octanol, hexanol, acetone or diethyl ether, in order to further ensure a specific morphology structure of the composite material, enhance uniform dispersibility of the modified phase material, better reduce polarization resistance of a cathode, improve output power of a battery, simplify preparation procedures, and enhance controllability and operability.
The invention is not particularly limited in principle for the specific selection of the metal salt, and the person skilled in the art can select and adjust the metal salt according to the practical application situation, the product requirement and the quality requirement, and the invention further ensures the specific morphology structure of the composite material, enhances the uniform dispersion of the modified phase material, better reduces the polarization resistance of the cathode, the metal salt preferably comprises one or more of metal nitrate, metal acetate, metal oxalate and metal carbonate, more preferably metal nitrate, metal acetate, metal oxalate or metal carbonate.
The specific choice of the pH adjuster is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to practical application conditions, product requirements and quality requirements, and the pH adjuster is preferably one or more of propionic acid, acetic acid, oxalic acid, ammonia water and sodium hydroxide, more preferably propionic acid, acetic acid, oxalic acid, ammonia water or sodium hydroxide, in order to further ensure a specific morphology structure of the composite material, enhance uniform dispersibility of the modified phase material, better reduce polarization resistance of a cathode, improve output power of a battery, simplify preparation procedures, and enhance controllability and operability.
The pH value of the precursor reaction solution is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to practical application conditions, product requirements and quality requirements, and the pH value of the precursor reaction solution is preferably 3-12, more preferably 5-10, and even more preferably 7-8 in order to further ensure the specific morphology structure of the composite material, enhance the uniform dispersibility of the modified phase material, better reduce the polarization resistance of the cathode, improve the output power of the battery, simplify the preparation process, and enhance the controllability and operability.
The preparation method is a complete and refined integral preparation process, further ensures the specific morphology structure of the composite material, enhances the uniform dispersion of the modified phase material, better reduces the polarization resistance of the cathode, improves the output power of the battery, simplifies the preparation process, enhances the controllability and the operability, and preferably further comprises a surfactant in the precursor reaction solution.
The specific selection of the surfactant is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to practical application conditions, product requirements and quality requirements, and the surfactant preferably comprises one or more of PVP, SDBS and CTAB, more preferably PVP, SDBS or CTAB, in order to further ensure a specific morphology structure of the composite material, enhance uniform dispersibility of the modified phase material, better reduce polarization resistance of a cathode, improve output power of a battery, simplify preparation procedures and enhance controllability and operability.
The concentration of the metal salt solution is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to practical application conditions, product requirements and quality requirements, and the concentration of the metal salt solution is preferably 0.001-0.5 mol/L, more preferably 0.1-0.4 mol/L, and even dispersibility of the modified phase material is further ensured, polarization resistance of a cathode is better reduced, output power of a battery is improved, preparation procedures are simplified, and controllability and operability are enhanced.
The volume ratio of the surfactant to the solvent is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to practical application conditions, product requirements and quality requirements, and the volume ratio of the surfactant to the solvent is preferably (0.001-0.3): 1, more preferably (0.05 to 0.25): 1, more preferably (0.1 to 0.2): 1.
The invention then places the solid oxide fuel cell or the electrode of the solid oxide fuel cell in the precursor reaction solution obtained in the above steps, and vacuumizes to obtain a reaction system.
The method is not particularly limited in principle, and a person skilled in the art can select and adjust the method according to practical application conditions, product requirements and quality requirements, and the method is used for further ensuring the specific morphology structure of the composite material, enhancing the uniform dispersibility of the modified phase material, better reducing the polarization resistance of a cathode, improving the output power of a battery, simplifying the preparation process and enhancing the controllability and the operability. In particular, when selecting an electrode of a solid oxide fuel cell or a half cell in a solid oxide fuel cell (symmetric cell for cathode, symmetric cell for anode), complete submersion may be selected; when a button cell and a flat-plate cell are selected, either full immersion or half immersion may be selected, i.e., only one electrode of the solid oxide fuel cell may be selected to be immersed.
The invention is not particularly limited in principle to the vacuum pressure of the vacuumizing treatment, and can be selected and adjusted by a person skilled in the art according to practical application conditions, product requirements and quality requirements, and in order to further ensure the specific morphology structure of the composite material, enhance the uniform dispersion of the modified phase material, the polarization resistance of the cathode is better reduced, the output power of the battery is improved, the preparation process is simplified, and the controllability and the operability are enhanced, wherein the vacuum pressure of the vacuumizing treatment is preferably less than or equal to 100KPa, more preferably less than or equal to 10KPa, and more preferably less than or equal to 1KPa.
And finally, the reaction system obtained in the steps is put into a reaction device for solvothermal reaction to obtain the modified solid oxide fuel cell electrode.
The temperature of the solvothermal reaction is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to practical application conditions, product requirements and quality requirements, and the solvothermal reaction temperature is preferably 100-300 ℃, more preferably 120-270 ℃, more preferably 120-240 ℃, more preferably 120-200 ℃ in order to further ensure the specific morphology structure of the composite material, enhance the uniform dispersibility of the modified phase material, better reduce the polarization resistance of a cathode, improve the output power of a battery, simplify the preparation process and enhance the controllability and operability.
The time of the solvothermal reaction is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to practical application conditions, product requirements and quality requirements, and the solvothermal reaction time is preferably 0.5-36 hours, more preferably 0.5-30 hours, more preferably 0.2-20 hours, and even more preferably 0.5-10 hours, in order to further ensure the specific morphology structure of the composite material, enhance the uniform dispersion of the modified phase material, better reduce the polarization resistance of the cathode, improve the output power of the battery, simplify the preparation process, and enhance the controllability.
The invention is in principle not particularly limited to the specific choice of the reaction device, and can be chosen and adjusted by the person skilled in the art according to the actual application, the product requirements and the quality requirements, in order to further ensure the specific morphology and structure of the composite material, the uniform dispersibility of the modified phase material is enhanced, the polarization resistance of the cathode is better reduced, the output power of the battery is improved, the preparation process is simplified, the controllability and the operability are enhanced, and the reaction device preferably comprises a hydrothermal reaction kettle.
The invention is a complete and refined integral preparation process, further ensures the specific morphology structure of the composite material, enhances the uniform dispersibility of the modified phase material, better reduces the polarization resistance of the cathode, improves the output power of the battery, simplifies the preparation process, enhances the controllability and the operability, and the invention grows nano particles on the surface of the solid oxide fuel cell in situ by a solvothermal method, and the preparation method of the modified solid oxide fuel cell electrode specifically comprises the following steps:
(1) Preparing a solvothermal solution according to the material to be modified;
(2) Soaking the battery in the solution, vacuumizing and performing solvothermal reaction;
(3) And taking the battery out of the solution, and cleaning the battery by using deionized water and ethanol to obtain the electrode modified by the nano particles.
More specifically:
(1) According to the material required by the modification phase, dissolving the required metal salt into a solvent according to a certain proportion, and adding acid or alkali according to the requirement to adjust the pH value of the solution to prepare a precursor solvothermal reaction solution; a surfactant can be further added to improve the solvothermal effect and the shape of the nano particles;
(2) Soaking the battery in a solvent hot solution, and performing vacuumizing treatment;
(3) Transferring the solution and the battery into a hydrothermal reaction kettle for in-situ solvothermal reaction, and growing the nano particles on the surface of the electrode in situ;
(4) And taking the battery out of the solution, repeatedly cleaning the battery with ethanol and deionized water until no residual powder exists on the surface of the battery, and obtaining the electrode structure modified by the nano particles.
The invention also provides a solid oxide fuel cell comprising an electrode;
the electrode comprises the modified solid oxide fuel cell electrode prepared by any one of the technical schemes or the preparation method of any one of the technical schemes.
The invention provides a modified solid oxide fuel cell electrode, an in-situ solvothermal preparation method thereof and a solid oxide fuel cell. The invention further reduces the resistance of the electrode on the premise of not changing the existing commercial solid oxide fuel cell material system, and is a method for in-situ modification of the solid oxide fuel cell electrode with high feasibility. According to the brand-new method for modifying the solid oxide fuel cell electrode, the nano particles are grown on the surface of the electrode in situ by a solvothermal method, the method is simple, the operation is easy, the morphology is controllable, the polarization impedance of the modified electrode is obviously reduced, and the output power of the cell is obviously improved. The modified solid oxide fuel cell electrode prepared by the invention has specific microscopic morphology and structure, specific single metal oxide, doped metal oxide or perovskite type catalytic material modified phase nano particles can be formed on the surface of the electrode, the polarization resistance of the modified electrode is obviously reduced, and the output power of the cell is obviously improved.
Experimental results show that nanoparticles with different morphologies such as nanospheres, nanocubes and the like can be grown on the surface of the electrode in situ by a solvothermal method, and the size of the nanoparticles can be controlled by regulating and controlling reaction conditions. The modified electrode has more excellent electrochemical performance than a blank electrode, and can reduce polarization resistance by more than 20%.
For further explanation of the present invention, the modified solid oxide fuel cell electrode, the preparation method thereof and the solid oxide fuel cell provided by the present invention are described in detail below with reference to examples, but it should be understood that these examples are implemented on the premise of the technical scheme of the present invention, and detailed implementation and specific operation procedures are given only for further explanation of the features and advantages of the present invention, and not limitation of the claims of the present invention, and the scope of protection of the present invention is not limited to the examples described below.
Example 1
(1) 0.25G of Ce (NO 3)3·6H2 O is dissolved in 30mL of ethylene glycol, 1mL of deionized water and 1mL of propionic acid are added, and the mixture is stirred until the solid is completely dissolved, so as to prepare a solution required by solvothermal;
(2) Putting a symmetrical battery with a structure of LSCF/GDC/YSZ/GDC/LSCF prepared in advance into a 50mL polytetrafluoroethylene lining, slowly pouring the solution obtained in the step (1) into the polytetrafluoroethylene lining, completely immersing the battery in the solution, and vacuumizing to-30 k Pa;
(3) Transferring the polytetrafluoroethylene lining in the step (2) to a stainless steel hydrothermal reaction kettle, and sealing the reaction kettle. Placing the reaction kettle in a baking oven, heating to 150-180 ℃, and preserving heat for 4 hours, wherein CeO 2 nano particles grow on the surface of an LSCF electrode in situ;
(4) And taking the symmetrical battery out of the solution, and repeatedly cleaning the symmetrical battery with deionized water and ethanol until the symmetrical battery is clear, thus obtaining the LSCF electrode containing CeO 2 nano particles.
The morphology and structure of the prepared modified solid oxide fuel cell composite cathode are characterized by a Scanning Electron Microscope (SEM) and an X-ray powder diffractometer (XRD) in the embodiment 1 of the invention, and the impedance spectrum (EIS) of the modified solid oxide fuel cell composite cathode is tested by a high-performance cell testing system for performance detection.
Referring to fig. 1, fig. 1 is a scanning electron microscope SEM image of the modified solid oxide fuel cell electrode prepared in example 1 of the present invention. Wherein, the graphs (a, b) are morphology graphs after being subjected to solvothermal treatment at 150 ℃ for 4 hours; fig. (c, d) are morphology images after being subjected to solvothermal treatment at 165 ℃ for 4 h; and (e, f) is a topography diagram after the solvent heat treatment at 180 ℃ for 4 hours.
As can be seen from fig. 1, the CeO 2 modified LSCF cathode prepared in this example 1 has a surface uniformly covered with a plurality of nanoparticles, has a spheroid-like morphology, and the size and coverage area of the nanoparticles vary with the temperature, and the higher the reaction temperature, the larger the nanoparticle size and the larger the coverage area. The in situ solvothermal method is described to enable uniform modification of nanoparticles at the electrode. And the morphology and parameters of the nano particles are changed by changing the parameters.
Referring to fig. 2, fig. 2 is an XRD diffractogram of the powder separated from the solvothermal solution in example 1 of the present invention.
All characteristic peaks on the graph can correspond to the CeO 2 PDF standard card one by one, which is shown in the figure 2, and the successful synthesis of the CeO 2 nano-particles is demonstrated.
Referring to fig. 3, fig. 3 is an arrhenius curve of polarization resistance of unmodified LSCF electrode and example 1 of the present invention after solvothermal treatment at different temperatures.
As can be seen from fig. 3, the polarization impedance of the LSCF electrode is significantly reduced after modification with CeO 2. The polarization resistance of the unmodified LSCF electrode is 0.338 Ω cm 2 at 750 ℃, after the hydrothermal treatment for 4 hours at 150 ℃ and 165 ℃ and 180 ℃, the polarization resistance of the modified LSCF electrode at 750 ℃ is respectively reduced to 0.227 Ω cm 2、0.2095Ω·cm2、0.219Ω·cm2, and the activation energy is obviously reduced compared with that of the unmodified LSCF electrode.
Example 2
(1) 0.25G of Ce (NO 3)3·6H2O、0.0284g Sm(NO3)3·6H2 O is dissolved in 30mL of ethylene glycol, 1mL of deionized water and 1mL of propionic acid are added, and the mixture is stirred until the solid is completely dissolved, so as to prepare a solution required by solvothermal;
(2) Putting a symmetrical battery with a structure of LSCF/GDC/YSZ/GDC/LSCF prepared in advance into a 50mL polytetrafluoroethylene lining, slowly pouring the solution obtained in the step (1) into the polytetrafluoroethylene lining, completely immersing the battery in the solution, and vacuumizing to-30 k Pa;
(3) Transferring the polytetrafluoroethylene lining in the step (2) to a stainless steel hydrothermal reaction kettle, and sealing the reaction kettle. Heating the reaction kettle to 180 ℃ in an oven, and preserving the heat for 2 hours, wherein Sm 0.1Ce0.9O2 nano particles grow on the surface of an LSCF electrode in situ;
(4) And taking the symmetrical battery out of the solution, and repeatedly cleaning the symmetrical battery with deionized water and ethanol until the symmetrical battery is clear, thus obtaining the LSCF electrode containing Sm 0.1Ce0.9O2 nano particles.
The polarization resistance of the modified solid oxide fuel cell composite electrode prepared in example 2 of the present invention was tested using a high performance electrochemical test device.
The results showed that the polarization resistance of unmodified LSCF was 0.587Ω & cm 2 at 750deg.C, and the polarization resistance of the electrode was reduced to 0.4998 Ω & cm 2 after modification.
Example 3
(1) 0.25G of Ce (NO 3)3·6H2O、0.0288g Gd(NO3)3·6H2 O is dissolved in 30mL of ethylene glycol, 1mL of deionized water and 1mL of propionic acid are added, and the mixture is stirred until the solid is completely dissolved, so as to prepare a solution required by solvothermal;
(2) Putting a symmetrical battery with a structure of LSCF/GDC/YSZ/GDC/LSCF prepared in advance into a 50mL polytetrafluoroethylene lining, slowly pouring the solution obtained in the step (1) into the polytetrafluoroethylene lining, completely immersing the battery in the solution, and vacuumizing to-30 k Pa;
(3) Transferring the polytetrafluoroethylene lining in the step (2) to a stainless steel hydrothermal reaction kettle, and sealing the reaction kettle. Placing the reaction kettle in a baking oven, heating to 180 ℃, and preserving heat for 4 hours, wherein Gd 0.1Ce0.9O2 nano-particles grow on the surface of an LSCF electrode in situ;
(4) And taking the symmetrical battery out of the solution, and repeatedly cleaning the symmetrical battery with deionized water and ethanol until the symmetrical battery is clear, thus obtaining the LSCF electrode containing Gd 0.1Ce0.9O2 nano particles.
Example 4
(1) 0.65G Co (NO 3)2·6H2 O is added into 20mL ethanol and magnetically stirred for 2h to obtain solution A;
(2) 0.128g of NaOH is added into 20mL of ethanol and stirred until the NaOH is completely dissolved, thus obtaining solution B;
(3) Slowly dripping the solution B into the solution A while stirring to obtain a black turbid liquid, and continuously stirring for 3 hours to obtain a solvothermal precursor solution;
(4) Putting a symmetrical battery with a structure of LSCF/GDC/YSZ/GDC/LSCF prepared in advance into a 50mL polytetrafluoroethylene lining, slowly pouring the solution obtained in the step (3) into the polytetrafluoroethylene lining, completely immersing the battery in the solution, and vacuumizing to-30 k Pa;
(5) Transferring the polytetrafluoroethylene lining in the step (2) to a stainless steel hydrothermal reaction kettle, and sealing the reaction kettle. Placing the reaction kettle in a baking oven, heating to 160 ℃, and preserving heat for 8 hours, wherein Co 3O4 nano-particles grow on the surface of an LSCF electrode in situ;
(6) And taking the symmetrical battery out of the solution, and repeatedly cleaning the symmetrical battery with deionized water and ethanol until the symmetrical battery is clear, thus obtaining the LSCF electrode with the Co 3O4 nano-particles on the surface.
The morphology and structure of the modified solid oxide fuel cell composite electrode prepared in example 4 of the present invention were characterized by Scanning Electron Microscopy (SEM).
Referring to fig. 4, fig. 4 is a SEM image of the surface of the Co 3O4 modified LSCF composite electrode prepared according to the present invention.
From fig. 4, it can be observed that a large number of nanoparticles are generated on the LSCF surface, and the nanoparticles are very uniform in size, about 50nm, and good in dispersibility.
Referring to fig. 5, fig. 5 is a high-magnification scanning electron microscope SEM image of the surface of the Co 3O4 -modified LSCF composite electrode prepared according to the present invention.
As can be seen from fig. 5, the nanoparticles generated on the LSCF surface have a cubic structure and are uniformly distributed.
Referring to fig. 6, fig. 6 is an XRD diffractogram of the powder separated from the solvothermal solution in example 4 of the present invention.
The powder obtained after the solvent hot solution is centrifuged and washed is characterized, and as can be seen from fig. 6, the characteristic peaks of the powder are in one-to-one correspondence with the Co 3O4 PDF standard card, which indicates that Co 3O4 is generated.
The modified solid oxide fuel cell cathode prepared in example 4 of the present invention was tested for performance using a high performance cell test system for impedance spectroscopy (EIS).
The result of testing polarization impedance of the high-performance electrochemical device shows that the polarization resistance of the unmodified LSCF electrode is 0.587Ω & cm 2 at 750 ℃, and after Co 3O4 modification, the polarization resistance at 750 ℃ is respectively reduced to 0.335 Ω & cm 2, thus greatly improving.
Example 5
(1) 0.25G of Ce (NO 3)3·6H2 O is dissolved in 30mL of ethylene glycol, 1mL of deionized water and 1mL of propionic acid are added, and the mixture is stirred until the solid is completely dissolved, so as to prepare a solution required by solvothermal;
(2) Putting a button cell with a structure of Ni-YSZ/YSZ/GDC/LSCF prepared in advance into a 50mL polytetrafluoroethylene lining, slowly pouring the solution obtained in the step (1) into the polytetrafluoroethylene lining, completely immersing the cell into the solution, and vacuumizing to-30 k Pa;
(3) Transferring the polytetrafluoroethylene lining in the step (2) to a stainless steel hydrothermal reaction kettle, sealing the reaction kettle, placing the reaction kettle in an oven, heating to 180 ℃, and preserving heat for 4 hours, wherein CeO 2 nano-particles are grown on the surfaces of an anode and a cathode at the same time in situ;
(4) And taking the symmetrical battery out of the solution, and repeatedly cleaning with deionized water and ethanol until the symmetrical battery is clear, so that the button battery with the anode and the cathode simultaneously modified by CeO 2 nano particles can be obtained.
Example 6
(1) 0.25G of Ce (NO 3)3·6H2 O is dissolved in 30mL of ethylene glycol, 1mL of deionized water and 1mL of propionic acid are added, and the mixture is stirred until the solid is completely dissolved, so as to prepare a solution required by solvothermal;
(2) Putting a button cell with a structure of Ni-YSZ/YSZ/GDC/LSCF-GDC prepared in advance into a 50mL polytetrafluoroethylene lining, slowly pouring the solution in the step (1) into the polytetrafluoroethylene lining to enable the cell to be completely immersed in the solution, and vacuumizing to-30 k Pa;
(3) Transferring the polytetrafluoroethylene lining in the step (2) to a stainless steel hydrothermal reaction kettle, and sealing the reaction kettle. Heating the reaction kettle to 180 ℃ in an oven, and preserving the temperature for 4 hours, wherein CeO 2 nano-particles grow on the surfaces of an anode and a cathode in situ at the same time;
(4) And taking the symmetrical battery out of the solution, and repeatedly cleaning with deionized water and ethanol until the symmetrical battery is clear, so that the button battery with the anode and the cathode simultaneously modified by CeO 2 nano particles can be obtained.
The above detailed description of a modified solid oxide fuel cell electrode and its in situ solvothermal preparation method, solid oxide fuel cell, and the principles and embodiments of the invention are described herein using specific examples, which are provided to aid in understanding the methods of the invention and its core concepts, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems, and performing any incorporated methods. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims. The scope of the patent protection is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal language of the claims.
Claims (10)
1. A method for preparing a modified solid oxide fuel cell electrode, comprising the steps of:
1) Mixing a metal salt solution and a pH regulator to obtain a precursor reaction solution;
2) Placing the solid oxide fuel cell or an electrode of the solid oxide fuel cell in the precursor reaction solution obtained in the steps, and vacuumizing to obtain a reaction system;
3) Putting the reaction system obtained in the steps into a reaction device, and performing solvothermal reaction to obtain a modified solid oxide fuel cell electrode;
the modified solid oxide fuel cell electrode comprises a solid oxide fuel cell electrode and modified phase nano particles compounded on the solid oxide fuel cell electrode;
the material of the modified phase nano-particles comprises single metal oxide and/or doped metal oxide;
The single metal oxide comprises CeO 2 and/or Co 3O4;
The doped metal oxide comprises Sm doped CeO 2 and/or Gd doped CeO 2;
the temperature of the solvothermal reaction is 100-300 ℃;
the solvothermal reaction time is 0.5-36 hours.
2. The method of manufacturing according to claim 1, wherein the solid oxide fuel cell electrode comprises an anode and/or a cathode of a solid oxide fuel cell;
The particle size of the modified phase nano particles is 10-300 nm;
The shape of the modified phase nanoparticle comprises one or more of nanospheres, nanocubes and nanoplatelets;
the complexing includes in situ growth.
3. The method according to claim 2, wherein the mass ratio of the modified phase nanoparticle to the solid oxide fuel cell electrode to which it is compounded is (1 to 30): 100.
4. The method of claim 1, wherein the modified phase nanoparticles are grown in situ on the solid oxide fuel cell electrode in a uniform dispersion.
5. The method of manufacturing according to claim 1, wherein the complexing on the solid oxide fuel cell electrode comprises complexing on a surface of the solid oxide fuel cell electrode and in a hole of the solid oxide fuel cell electrode;
the modified phase nano particles form a modified phase nano particle layer which is coated on the surface of the solid oxide fuel cell electrode and the surface of the hole of the solid oxide fuel cell electrode.
6. The method of manufacturing according to claim 1, wherein the solid oxide fuel cell comprises one or more of a cathode symmetrical cell, an anode symmetrical cell, a button cell and a flat plate cell.
7. The production method according to claim 1, wherein the solvent of the metal salt solution comprises a mixed solvent of an organic solvent and water or an organic solvent;
the metal salt comprises one or more of metal nitrate, metal acetate, metal oxalate and metal carbonate;
the pH regulator comprises one or more of propionic acid, acetic acid, oxalic acid, ammonia water and sodium hydroxide;
the pH value of the precursor reaction solution is 3-12;
the precursor reaction solution also comprises a surfactant.
8. The method of claim 7, wherein the organic solvent comprises one or more of ethanol, ethylene glycol, glycerol, octanol, hexanol, acetone, and diethyl ether;
The surfactant comprises one or more of PVP, SDBS and CTAB;
The concentration of the metal salt solution is 0.001-0.5 mol/L;
The volume ratio of the surfactant to the solvent is (0.001-0.3): 1, a step of;
The disposing includes full immersion or half immersion.
9. The production method according to claim 1, wherein the vacuum pressure of the vacuuming treatment is 100KPa or less;
the reaction device comprises a hydrothermal reaction kettle.
10. A solid oxide fuel cell comprising an electrode;
The electrode comprises the modified solid oxide fuel cell electrode prepared by the preparation method of any one of claims 1 to 9.
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